Dyestuffs of the anthraquinone series



Patented June 10, 1941 UNITED STATES PATENT OFFICE DYESTUFFS OF THE ANTHRAQUINONE SERIES Fritz Baumann and Heinz-Werner Schwechteh, Leverkusen I. G.-Werk, Germany, assignor to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing.

' Serial No. 194,602.

The present invention relates to new dyestufis of the anthraquinone-acridone series.

We have found that new dyestuffs of the anthraquinone-acridone series can be obtained by causing aromatic amines having at least one exchangeable hydrogen atom to react with a-arylamino anthraquinone 2.1 (N) 1.2' (N) acridones which contain carboxylic acid groups in form of their corresponding acid. halides. Preferably those a-arylamino-anthraquinone- 2.1-(N)-1.2'-(N)-acridones are used as starting materials which have the carboxylic acid group in the aryl nucleus and which correspond to the general formula wherein A stands for an anthraquinone-benz acridone or anthraquinone-naphthacridone ring Original application March 8, 1938,

Divided and this application March 7, .1940, Serial No. 322,772. In Germany March 17, 1937 4 Claims. (Cl. 260-277) 1'.2?-(N)-acridone upon a halogen-aryl-ca'rboxylic acid ester, as, for instance, a p-, mor o-halogen benzoic acid methylor ethyl-ester or a halogen-naphthoic acid ester. In the reaction product thus obtained the acid ester group is saponified in the usual way, and the carsystem and the Greek letter a. means that the nitrogen atom is attached in alpha-positionto the anthraquinone nucleus of the anthraquinoneacridone ring system. Compounds of this kind are, for instance, anthraquinone-2.1-(N) -1.2"- (N) benzene acridone 4 [anilido p carboxylio acid chloride], anthraquinone-2.1-(N) 1.2' (N) benzene acridone 4 [anilido m-carboxylic acid chloride], 4-chlororesp. 5'- chloro anthraquinone 2.1 (N) 1.2 (N) benzene acridone 4 [anilido p carboxylic acid chloride], 4'-chlororesp. 5'-chloro-anthraquinone 2.1 (N) 1.2' (N) benzene acridone' 4 [anilido m carboxylic acid chloride], 3.5' dichloro-anthraquinone -2.1 (N) 1'.2f (N) benzeneacridone '4 [anilido p-carboxylic acid chloride], anthraquinone-2.1- (N) 1.2 (N) benzene-acridone"- 51'-"[anilido-p-carboxylic acid chloride], 3;5'-diehloroanthraquinone 2.1- (N) 1'.2' -'(N) benzene acridone 5 [anilido p carboxylic acid chloride], 5 chloro-anthraquinone 2.1- (N) 1'.2' (N) benzene acridone; 8 [anilido m-carboxylic acid chloride], and anthraquinone- 2.1 (N) 1'.2 (N) naphthacridone 5 [anilido-p-carboxylie acid chloride].

The a aryl amino anthra'quinone-2.1 (N) -1.2'-(N) -acridonecarboxylic acidsused as starting materials can be obtained, for example,

'by' reacting an .a-anuno anthraquinone-2J-(N) '1.4-diamino-anthraquinone, amino -'4.8 dihydroxy anthraquinone, 5 amino 1.9 anthrapyrimidine, 5 amino 4'- boxylic acid so formed is treated with agents being capable of forming acid halides such as .thionyl-chloride.

Another type of starting materials is obtained by causing anthraquinone-1.4-dihalogen-2-caramino-benzoic acid esters.

As amines having at least 1 exchangeable hydrogen atom there come into consideration aromatic amines as well as those which are derived from vattable compounds. Especially amines which are derived from compounds with the anthraquinone ring system are used. Such amines are, for instance, l-amino-anthraquinone, 1 amino 4 benzoylamino anthraquinone, 1 amino 5 benzoylamino-anthraquinone,

1-benzoylamino-5- bonzoylamino 1.1 anthrimide carbazole,

-2 amino 3 hydroxy anthraquinone, 1

amino 2 hydroxy anthraquinone, 2 amino 3 mercapto anthraquinone, 2 amino l -mercapto anthraquinone, 1.2 diamino anthraquinone, 1-a1kyl(resp. aryl) amino 2 amino-anthraquinone. In cases where an aminoanthraquinone is used bearing in o-position to the amino group an OH-, SH- or NI-IR-group (R being hydrogen, alkyl, or aryl), a ring formation takes place and an oxazole, thiazole or imidazole ring system results' The reaction of the carboxylic acid halides with the amines is carried out at an elevated temperature and in the amine itself as solvent or in the presence of an indifferent solvent such as o-dichloro-benzene, trichloro-benzene, nitro-benzene, chloro-naphthalene, or ethyl-carbazole.

In case an amino-anthraquinone is used bearing in o-position a group being capable of forming a ring with the amino group (an OH-, SH- or NHR-group) the reaction temperature reached, for instance, by working in nitrobenzene is not sufficient in order to effect the splitting off of water and ring formation. In these cases an additional heating of the first formed reaction product in a high boiling solvent as, for instance.

ethyl-carbazole is necessary.

The products thus obtained are vat dyestuffs which if prepared from a-arylamino-anthraquinone-2.1- (N) -1 .2- (N) -acridone carboxylic acids having the aryl radical in i-position dye cotton yellowish green shades, but it prepared from the same acids having the aryl radical in or 8-position dye cotton violet-brown to black-brown shades. The new dyestuffs sho'w excellent fastness properties and in particular they are extremely fast to light. They are difficultly soluble in organic solvents but can be recrystallized from quinoline. They dissolve in concentrated sulfuric acid with brown color. The color of the vat is reddish violet to reddish brown.

This application is a divisional application of our U. S. application Ser. No. 194,602, filed March 8, 1938.

The following examples illustrate the invention, without, however, restricting it thereto, the parts being by weight.

Example 1 11 parts of a-amino-anthraquinone are heated in 800 partsof nitrobenzene up to 120 C.; at this temperature 24 parts of 3'.5'-di-chloro-anthraquinone-2.1-(N) 1'.2' (N) benzene acridone-4- [anilido-p-carboxylic acid chloride] are added to the solution and then stirred at 130 C., until the evolution of hydrochloric acid has ceased. The dyestufi is filtered with suction at 90 C., washed with nitrobenzene and then dried. The green dye-powder shows a Bordeaux-red color of the vat and dyes cotton green shades.

By using l-aminc-5-benzoyl-amino-anthraquinone instead of u-amino-anthraquinone a prodnot is obtained which dyes cotton yellowish to 1 olive green; 4amino-1.9-anthrapyrimidine also yields an olive green dyestuff. On the other hand, when reacting the acid achloride with 4-amino-5'-chloro anthraquinone-2.1-(N) -1.2- (N) -benzene-acridone, a dyestufi is obtained which dyes vegetable fiber greenish blue.

The carboxylic acid chloride used in the reac- .tion is obtained, for example, by the condensa- 5 parts of 3'-5'-dichloro-anthraquinone-2.1- (N) -1.2'-(N) benzene acridone-i-[anilido-incarboxylic acid chloride] obtained according to Example 1 are slowly heated to boiling with 2.5 parts of a-amino-anthraquinone in 160 parts of anhydrous trichloro-benzene. When the carboxylic acid chloride is transformed the difficultly soluble dyestuff is filtered with suction at 120 C., washed with pyridine and dried. The substance crystallizing in green needles dyes cotton from the vat green shades.

Example 3 26 parts of 5'-chloro-anthraquinone-2.1-(N)- 1'.2- (N) -|benzene acridone-- [anilido p carlboxylic acid chloride] obtainable in an analogous manner as the product of Example 1 and 12 parts of 2.3-amino-hydroxy-anthraquinone are heated to boiling for some hours in 800 parts of nitrobenzene. When the solution is still warm the dyestu'ff is filtered with suction, washed with nitrobenzene and then dried.

The substance being still alkali-sensitive is subsequently heated to boiling in ethyl-carbazole for ashort time, the reaction mixture is diluted with pyridine and the dyestuff filtered off at C. In this way the dyestuff of the following constitution '2-1-oxazole is obtained which dyes-cotton strong greenish olive shades.

By using a higher boiling solvent in the reaction instead of nitrobenzena'the pure oxazole is obtained immediately.

"Example 4 A mixture off'13 parts of 5-cliloroanthraqui'- none-2.1-(N) 1'.2' N) benzene acri'donei- [anilido-p-carboxylic acid chloride] and '7 parts of 2-amino 3 mercapto-anthraquinone' is added to 100 parts of a-chloro-naphthalene at 120-130 C., whereupon the reaction mixture is slowly heated to 260 C. At the \boiling temperature green needles separate from the green solution. The solution is heated to boiling for about 30 minutes and the "green dyestuff 'i's filtered off 'at C. After drying the dyestufi is obtained in form of a green powder which, after being crystallized from quinoline, dyes cotton from the vat yellow-greenshades.

When reacting '4 chloro=anthraquinone-2;1- (N) -1' .2 (N) -b'enzene -"acridone -4 [anilido -pcarboxylic acid chloride] upon 2-amino-3 'mer- "captoanthra'.quinone' a thiazole is obtained which Thedyestufibbtainable'in the same manner which has the following constitution dyes cotton bluish green shades.

The thiazoles obtainable from l-mercapto-2- amino-anthraquinone represent olive green dye- 2 stuifs.

. Example 5 By causing to react 26 parts of 5'-chloro-antraquinone-2.1-(N) -1' .2'- (N) -benzene-acridone- 4-[anilido-p-carboxylic acid chloride] upon 18 parts of l-anilido-Z-amino-anthraquinone in 40 parts of a-chloro-naphthalene at a temperature of 260 C. for one hour a dyestufi of the following constitution is obtained which is filtered with suction at room temperature. It can be recrystallized from nitrobenzene and dyes cotton green shades from the vat.

Example 6 is obtained in form of red-brown needles. The

dyestufi is soluble in concentrated suliuricacid with yellow-br'own color. It dyes vegetable fiber from. bluish red vat black-brown shades.

By: using -anthraquinone-2.1-(N) -l'.2'-(N)- benzeneacridone"-5- [anilidop carboxylic acid chloride] resp. anthraquinone-2.1-(N) -1'.2'-(N) naphtha acridone-b- [anilido p -carboxylic acid chloride] instead .of 3.5'-dichloro-anthraquinone-2.1- (N) -1.2- (N) -benzene.- acridone-5- [anilido-p-carboxylic acid chloride] dyestufis are obtained which yield on vegetable fiber shades similar to those obtainable by the above dyestufi.

By using l-hydroxv-2-amino-anthraquinone resp. 1-amino-2-mercapto-anthraquinone instead of 1amino-2-hydroxy-anthraquinone, the corresponding oxazoles or thiazoles are obtained which show similar dye-properties.

By using as starting material 2-amino-3-hydroxy-anthraquinone and 3'.5-dichloro-anthraquinone-2.1- N) -1'.2'- (N) benzene-acridone-5- 0 ianilido-p-carboxylic acid chloride] products are obtained yielding greyish colors.

Example 7 55 parts of 3.5'-dichloro-anthraquinone-2.1- (N) -1.2'-(N) -benzene' acridone 5 [anilido-pcarboxylic acid chloride] and 25.5 parts of l-mercapto-2-amino-anthraquinone are slowly heated in 1500 parts of chloro-naphthalene to the boilingpoint of chloro-naphthalene and stirred for about one hour at this temperature. The reaction product is isolated at room temperature in the usual manner.

When the reaction product is heated in ethylcarbazole and precipitated with pyridine the dyestuff is obtained in form of black-brown needles. It dyes cotton from red-violet vat nigger-brown shades. The solution in sulfuric acid is yellowbrown.

Example 8 5 parts of 5'-chloroanthraquinone-2.1-(N) 1'.2'- (N) -benzene-acridone-4-[anilido-p-carboxylic acid chloride] and 5 parts of dehydrothiotoluidine are heated to boiling in parts of nitrobenzene for about hour, whereby the corresponding acylamine crystallizing in long fine needles is obtained, hydrogen chloride being split oflf. The product can be worked up in the usual manner; it is soluble in sulfuric acid with yellow color and precipitates in clear green flakes after diluting the sulfuric acid solution with water.

The product can be used as pigment after suitable formation. This application is a division of our application Serial No. 194,602, filed March 8, 1938.

We claim:

1. The compounds of the formula wherein A stands for an anthraquinone-acridone selected from the group consisting of the benzand naphth-acridones, the Greek letter a means that the nitrogen atom is attached in alpha-position to the anthraquinone nucleus of the anthraquinone acridone ring system and R stands for a vattable p-quinoidic radical containing at least 3 condensed rings.

2. The compounds of the formula a H ArNGdJI-R wherein A stands-for an anthraquinone acridone selected from the group consisting of-v the henze and -naphth-ac-ridones, the Greek letter means that the nitrogen atomis. attached. inralphat-position to the anthraquinonenucleus of the anthraquinone LacridQne' ringsystem and R stands for avattable p.-quinoidie radical containing. at least -3 condensedrings.----

1 3; The compoundsof the: formula t whe re in A standsfor an anthraquirjiohe-aqridone selected ff'c'pm" the grbup'cpn's'isting of vthe benza'nd" "n'aphth-acrid'one's, and tfi Greek letter oc means that the'nitro'g'en atom is attached in alpha-position t6 the anthraquinone nucleus of the anthraquinone-acridone l ing system.

' Thecompoundofthe following formula FRITZ BAUMAN N.

v HEINZ-WERNER SCHWECHTEN. 

